JP2013065813A - Imprint system and maintenance method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an imprint system which improves the accuracy of an imprint device and a maintenance method of the imprint system.SOLUTION: An imprint system includes: a liquid discharge head 24 including a nozzle plate 23A where a nozzle discharging a functional liquid is formed; relative movement means relatively moving a substrate and the liquid discharge head 24; transfer means transferring an irregular pattern of a mold to a surface of the substrate where the functional liquid is applied; curing means curing the functional liquid with the mold contacting with the functional liquid; first temperature control means 44, 46 controlling a temperature of the nozzle plate 23A; and second temperature control means 42, 48 controlling a temperature of at least one surface of the liquid discharge head 24 which is other than the nozzle plate 23A. The above problem is solved by the imprint system and a maintenance method of the imprint system.

Description

  The present invention relates to an imprint system and an imprint system maintenance method, and more particularly, to a liquid application technique for applying a functional liquid onto a medium such as a substrate by an ink jet method.

  In recent years, with the miniaturization and high integration of semiconductor integrated circuits, as a technique for forming a fine structure on a substrate, a desired uneven pattern to be transferred to a resist (UV curable resin) disposed on the substrate is formed. The resist is cured by irradiating ultraviolet rays in a state of pressing the molded mold, and the mold is separated (released) from the resist on the substrate, thereby transferring the fine pattern formed on the mold to the substrate (resist). Nanoimprint methods are known.

  As a form for applying an imprint material (resist liquid) to a substrate, a system to which an ink jet method is applied has been proposed. For example, Patent Document 1 described below describes an apparatus that includes a print head having a plurality of nozzles, discharges an imprintable medium from the nozzles, and performs imprint lithography.

JP 2010-183106 A

  In a system to which an ink jet method is applied as described in Patent Document 1, in order to discharge an imprintable medium from a nozzle, ink viscosity is adjusted, droplet amount is controlled, and ejection stability is ensured. There was a need to do. The ink viscosity has been conventionally controlled by adjusting the temperature of the head.

  In nanoimprint, it is known that throughput is improved by making droplets smaller and placing them densely on the substrate. To improve throughput, the head temperature is adjusted to control the ink viscosity. It was important to adjust.

  However, if there is a difference between the head temperature and the ambient temperature, in the imprint system, the device or the substrate is displaced due to the difference in linear expansion, the positional relationship between the mold and the substrate is displaced, and the imprint accuracy is lowered. There was a problem.

  The present invention has been made in view of such circumstances, and it is possible to adjust the temperature of the head from the viewpoint of ejection and to keep the accuracy of the imprint apparatus by minimizing the temperature difference between the head and the surroundings. An object of the present invention is to provide an imprint system and an imprint system maintenance method.

  In order to achieve the above object, the present invention includes a nozzle plate on which nozzles for discharging a functional liquid onto a substrate are formed, and pressurizes the functional liquid in a pressure chamber communicated with the nozzle. A predetermined concavo-convex pattern is formed on a surface of the substrate on which the functional liquid has landed, a liquid discharge head provided with a piezoelectric element, relative movement means for relatively moving the substrate and the liquid discharge head. Transfer means for transferring the concavo-convex pattern of the formed mold, curing means for curing the functional liquid in a state where the entire surface of the mold on which the concavo-convex pattern is formed is in contact with the functional liquid, and First temperature control means for controlling the temperature of the nozzle plate and a cover for covering at least one surface other than the nozzle plate of the liquid discharge head are provided, and the temperature of the cover A second temperature control means for controlling to provide an imprint system, characterized in that it comprises a.

  According to the present invention, the first temperature control means for controlling the temperature of the nozzle plate and the second temperature control means for controlling the temperature of the cover covering at least one surface of the liquid discharge head are provided. Thus, by controlling the temperature of the nozzle plate with the first temperature control means, the temperature of the discharged functional liquid can be controlled, and the functional liquid can have a desired viscosity. Accordingly, it is possible to improve the discharge accuracy and discharge the fine droplets.

  In addition, since the temperature of the cover covering at least one surface other than the nozzle plate of the liquid discharge head is controlled by the second temperature control means, the nozzle is used to heat the temperature of the functional liquid by the first temperature control means. Even if the plate and the liquid discharge head are warmed, the second temperature control means can achieve a desired temperature. Therefore, the heat generated by the first temperature control means can be prevented from being transmitted to another device through the liquid discharge head, and imprinting can be performed without causing the substrate to expand or warp. Therefore, the imprint accuracy can be improved.

  In the imprint system according to another aspect of the present invention, the first temperature control means includes means for controlling the temperature of the side surface of the liquid discharge head, and controls the temperature of the functional liquid in the liquid discharge head. It is preferable to control.

  According to the imprint system according to another aspect of the present invention, since the temperature of the side surface of the liquid discharge head is controlled by the first temperature control unit, the temperature of the functional liquid in the pressure chamber can be controlled. it can. Therefore, since the functional liquid can be set to a desired temperature, it is possible to improve discharge accuracy and discharge fine droplets.

  In the imprint system according to another aspect of the present invention, the second temperature control unit covers the surface other than the nozzle plate of the liquid discharge head and the first temperature control unit, and distributes the temperature control liquid. It is preferable that the liquid discharge head cover has a flow path.

  According to the imprint system according to another aspect of the present invention, since the liquid discharge head cover that covers the surface other than the nozzle plate of the liquid discharge head is provided, the heat of the heated liquid discharge head is transmitted to another device. This can be prevented. Further, as a second temperature control means, a flow path is provided in the liquid discharge head cover, and a temperature control fluid is allowed to flow, thereby effectively preventing the heat of the liquid discharge head from being transmitted to other devices. Can do.

  In an imprint system according to another aspect of the present invention, the nozzle is preferably formed of silicon.

  According to the imprint system according to another aspect of the present invention, since the nozzle is made of silicon, the radiant heat can be lowered, and the temperature change to the substrate on which the functional liquid droplets are discharged can be reduced. Can do. Therefore, functional droplets can be discharged with high accuracy.

  The imprint system according to another aspect of the present invention preferably includes a nozzle cover that covers a portion of the nozzle plate where the nozzle is not formed.

  According to the imprint system according to another aspect of the present invention, since the nozzle cover that covers the portion of the nozzle plate where the nozzles are not formed is provided, the substrate is subjected to convection and heat dissipation from portions other than the nozzle of the nozzle plate. Heat can be prevented from being transmitted. Therefore, deformation of the substrate can be prevented and imprint accuracy can be improved.

  In the present invention, the “portion where the nozzle is not formed” is a portion where functional liquid droplets can be discharged without any problem even when covered with a head cover.

  In the imprint system according to another aspect of the present invention, it is preferable that the nozzle cover is formed at a position closer to the substrate than the nozzle plate.

  According to the imprint system according to another aspect of the present invention, since the nozzle cover is formed at a position closer to the substrate than the nozzle plate, it is possible to efficiently prevent the heat of the nozzle plate from being transmitted to the substrate.

  In the imprint system according to another aspect of the present invention, it is preferable that a vacuum is provided between the nozzle plate and the substrate.

  According to the imprint system according to another aspect of the present invention, it is possible to prevent the heat of the head from moving to the substrate by convection by creating a vacuum between the nozzle plate and the substrate. Therefore, the substrate can be prevented from being deformed by heat, and the imprinting accuracy can be improved.

  In order to achieve the above object, the present invention provides a maintenance method for an imprint system as described above, wherein a functional liquid discharging step for purging the functional liquid, and the nozzle plate through the functional liquid discharging step. An absorbing step for bringing the functional liquid adhering to contact the blot member to absorb the functional liquid, and the droplet adhering to the nozzle plate has a height higher than the thickness of the nozzle cover. An imprint system maintenance method is provided which is formed so as not to contact the nozzle cover.

  In the imprint system described above, since the nozzle cover is provided in a portion of the nozzle plate where the nozzles are not formed, a step structure is formed between the nozzle plate and the nozzle cover. According to the present invention, the height of the liquid droplets ejected during the functional liquid discharging process at the time of maintenance is equal to or greater than the thickness of the nozzle cover, so that the liquid droplets are easily removed by being absorbed by the blot member. be able to. Further, by discharging the liquid so as not to come into contact with the nozzle cover, it is possible to prevent the liquid droplet from overflowing from the nozzle cover by staying on the nozzle plate.

  In the imprint system maintenance method according to another aspect of the present invention, it is preferable that the blot member and the droplet discharge head are relatively moved after the blot member is brought into contact with the functional liquid. .

  According to the imprint system maintenance method according to another aspect of the present invention, since the blot member is moved relatively after being brought into contact with the functional liquid, the liquid can be effectively absorbed. .

  A maintenance method for an imprint system according to another aspect of the present invention includes a third temperature control unit that controls the temperature of the blot member, and controls the temperature of the blot member to substantially the same temperature as the substrate. Is preferred.

  When absorbing droplets adhering to the nozzle plate, the heat of the nozzle plate is transmitted to the blot member, and may be transferred to other devices of the imprint system by convection and heat dissipation. In this case, the substrate may be transferred to the substrate and deformed, and the imprinting accuracy is lowered. According to the imprint system maintenance method according to another aspect of the present invention, the third control means for controlling the temperature of the blot member is provided, and the temperature of the blot member is controlled to be substantially the same as that of the substrate. The heat of the blot member is transmitted to the substrate, and the substrate can be prevented from being deformed.

  Note that “substantially the same temperature as the substrate” means that the temperature difference from the substrate is within ± 0.1 ° C.

  A maintenance method for an imprint system according to another aspect of the present invention includes a capping member that covers the nozzle when the liquid ejection head is on standby, the capping member contacting the nozzle cover, It is preferable to perform capping.

  According to the imprint system maintenance method according to another aspect of the present invention, the heat of the nozzle plate is transferred to the capping member by bringing the capping member into contact with the nozzle cover, and heat is transferred from the capping member to other devices and substrates. It is possible to prevent transmission.

  In the imprint system maintenance method according to another aspect of the present invention, the capping member is provided with fourth temperature control means for controlling the temperature of the capping member, and the temperature of the capping member is substantially the same as that of the substrate. It is preferable to control to the temperature of.

  According to the imprint system maintenance method according to another aspect of the present invention, the capping member includes the fourth temperature control means, and the temperatures of the capping member and the substrate are substantially the same. It is possible to prevent the substrate from being deformed by being transmitted to the substrate.

  According to the imprint system and the imprint system maintenance method of the present invention, by controlling the temperature of the functional liquid with the first temperature control means, it is possible to improve the discharge accuracy and enable fine droplet discharge. it can. In addition, the second temperature control unit can prevent the heat generated by the first temperature control unit from being transmitted to other devices and substrates, so that the imprinting accuracy can be improved. Further, even during maintenance, it is possible to prevent heat from being transmitted to other devices and substrates, so that droplets can be discharged with high accuracy.

It is a figure explaining each process of the nanoimprint system concerning the present invention. 1 is an overall configuration diagram of a nanoimprint system according to the present invention. It is a block diagram which shows schematic structure of the photocurable resin liquid discharge part shown in FIG. It is a top view which shows the structural example of the inkjet head shown in FIG. It is sectional drawing which shows the three-dimensional structure of the inkjet head shown in FIG. FIG. 2 is a perspective view (a) and a cross-sectional view (b) of an inkjet head and a head cover. They are the perspective view (a) and sectional drawing (b) of the inkjet head and head cover which concern on other embodiment. It is sectional drawing of an inkjet head provided with a nozzle cover. It is sectional drawing of an inkjet head provided with the nozzle cover which concerns on other embodiment. It is sectional drawing of the droplet of the nozzle surface discharged | emitted by purge. It is a top view on the nozzle surface where the droplet shown in FIG. 10 adhered. It is sectional drawing of other embodiment of the droplet of the nozzle surface discharged | emitted by purge. It is a top view of the nozzle surface to which the droplet shown in FIG. 12 adhered. It is explanatory drawing explaining the state in which a blot member absorbs a droplet. It is a perspective view of a blot member. It is a perspective view of a capping member. It is explanatory drawing which shows the state which the capping member contacted the nozzle plate.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

[Description of nanoimprint method]
First, the nanoimprint method according to the embodiment of the present invention will be described step by step with reference to FIGS.

  In the nanoimprint method shown in this example, a concavo-convex pattern formed in a mold (a mold, for example, a Si mold) is applied to a photocurable resin liquid (functional liquid, for example, a resist liquid) formed on a substrate (quartz substrate or the like). Is transferred to the cured photocurable resin layer, and a fine pattern is formed on the substrate using the photocurable resin layer as a mask pattern.

  First, a quartz substrate 20 (hereinafter also simply referred to as “substrate”) shown in FIG. The substrate 20 shown in FIG. 1A has a hard mask layer 21 formed on the front side surface 20A, and a fine pattern is formed on the front side surface 20A. The board | substrate 20 should have predetermined | prescribed permeability | transmittance which permeate | transmits light, such as an ultraviolet-ray, and thickness should just be 0.3 mm or more. By having light transmittance, exposure from the back side surface 20B of the substrate 20 becomes possible.

As a substrate 20 applied when using a Si mold, a substrate whose surface is coated with a silane coupling agent, a laminate of metal layers made of Cr, W, Ti, Ni, Ag, Pt, Au, etc., CrO ₂ , WO ₂ , those obtained by laminating metal oxide film layers made of TiO _{2 and the} like, and those obtained by coating the surface of these laminates with a silane coupling agent.

  That is, the hard mask layer 21 illustrated in FIG. 1A uses a laminate (covering material) such as the above metal film or metal oxide film. If the thickness of the laminate exceeds 30 nm, the light transmittance is lowered, and the photocurable resin is liable to be hardened. Therefore, the thickness of the laminate is 30 nm or less, preferably 20 nm or less.

  “Predetermined permeability” means a liquid having a function of forming light on the surface when light irradiated from the back side surface 20B of the substrate 20 is emitted from the front side surface 20A (for example, reference numeral 25 is attached to FIG. 1B). For example, the transmittance of light having a wavelength of 200 nm or more irradiated from the back side surface is preferably 5% or more.

  Further, the structure of the substrate 20 may be a single layer structure or a laminated structure. As the material of the substrate 20, other than quartz, silicon, nickel, aluminum, glass, resin, or the like can be used as appropriate. These materials may be used individually by 1 type, and may synthesize | combine and use 2 or more types suitably.

  When a material other than quartz is used for the substrate 20, quartz is used as the material for the mold (symbol 26 in the figure and the figure), and exposure is performed from the mold side.

  The thickness of the substrate 20 is preferably 0.05 mm or more, and more preferably 0.1 mm or more. If the thickness of the substrate 20 is less than 0.05 mm, the substrate side may be bent when the pattern forming body and the mold are in close contact, and a uniform contact state may not be ensured. In view of avoiding breakage due to pressing during handling or imprinting, it is more preferable that the thickness of the substrate 20 is 0.3 mm or more.

  A plurality of photocurable resin liquids 25 containing a photocurable resin are discretely discharged from the inkjet head 24 onto the front side surface 20A of the substrate 20 (FIG. 1B: discharge process). As used herein, the term “discretely ejected droplets” refers to a plurality of droplets that have landed at a predetermined interval without contacting other droplets that have landed on adjacent landing positions on the substrate 20. doing.

  In the discharging step shown in FIG. 1B, the pressure chamber (shown with reference numeral 32 in FIG. 5) provided in the inkjet head 24 is expanded and then contracted to discharge the photocurable resin liquid in the pressure chamber. I am letting.

  Moreover, the discharge amount and arrangement density of the photocurable resin liquid 25 are preset (adjusted). For example, the discharge amount and the arrangement density are relatively large in a region where the concave volume of the concave and convex pattern of the mold (shown by reference numeral 26 in FIG. 1C) is large, and the spatial volume of the concave portion is small. In an area where there is no recess, the adjustment is made to be relatively small. After the adjustment, the photocurable resin liquid 25 is arranged on the substrate 20 according to a predetermined arrangement pattern.

  After the ejection step shown in FIG. 1B, the photocurable resin liquid 25 on the substrate 20 is pressed by pressing the concave / convex pattern surface of the mold 26 on which the concave / convex pattern is formed to the front side surface 20A of the substrate 20 with a predetermined pressing force. A photocurable resin layer 25 ′ composed of a combination of a plurality of photocurable resin liquids 25 wetted and spread is formed (FIG. 1C: photocurable resin layer forming step).

  In the photocurable resin layer forming step, the residual gas can be reduced by pressing the mold 26 against the substrate 20 after the atmosphere between the mold 26 and the substrate 20 is reduced in pressure or vacuum.

  However, in a high vacuum atmosphere, the photocurable resin layer 25 ′ before curing is volatilized and it may be difficult to maintain a uniform film thickness. Therefore, the residual gas can be reduced by changing the atmosphere between the mold 26 and the substrate 20 to a helium (He) atmosphere or a reduced pressure He atmosphere. Since He passes through the quartz substrate 20, the residual gas (He) taken in gradually decreases. Since it takes time to permeate He, it is more preferable to use a reduced pressure He atmosphere.

  The pressing force of the mold 26 is in the range of 100 kPa to 10 MPa. A relatively large pressing force promotes the flow of the resin, promotes the compression of the residual gas, dissolves the residual gas in the photocurable resin, and permeates the He in the substrate 20 and leads to a tact-up.

  However, if the pressing force is too large, foreign matter may be caught when the mold 26 comes into contact with the substrate 20, and the mold 26 and the substrate 20 may be damaged. Is done.

  The range of the pressing force of the mold 26 is more preferably 100 kPa to 5 MPa, and still more preferably 100 kPa to 1 MPa. The reason why the pressure is 100 kPa or more is that when imprinting is performed in the atmosphere, the space between the mold 26 and the substrate 20 is filled with the photocurable resin liquid 25, and the space between the mold 26 and the substrate 20 is large. This is because the pressure is applied at atmospheric pressure (about 101 kPa).

  Thereafter, ultraviolet light is irradiated from the back side surface 20B of the substrate 20 to expose the photocurable resin layer 25 ′, thereby curing the photocurable resin layer 25 ′ (FIG. 1C: photocurable resin layer). Curing step). In this example, the photocuring method in which the photocurable resin layer 25 ′ is cured by light (ultraviolet rays) is exemplified, but a thermosetting resin liquid layer is formed using a liquid containing a thermosetting resin, and heated. Other curing methods such as a thermosetting method of curing the thermosetting resin liquid layer may be applied.

  After the photocurable resin layer 25 ′ is sufficiently cured, the mold 26 is peeled from the photocurable resin layer 25 ′ (FIG. 1D: peeling process). The mold 26 may be peeled off as long as the pattern of the photocurable resin layer 25 ′ is not easily damaged. The mold 26 may be peeled off gradually from the edge of the substrate 20 or peeled off while pressing from the mold 26 side. The mold 26 can be peeled off by reducing the force applied to the photocurable resin layer 25 ′ on the boundary line where the mold 26 peels from the photocurable resin layer 25 ′ (pressure peeling method). .

  Further, the vicinity of the photocurable resin layer 25 ′ is heated to reduce the adhesion between the photocurable resin layer 25 ′ and the surface of the mold 26 at the interface between the mold 26 and the photocurable resin layer 25 ′. In addition, it is also possible to apply a method (heat-assisted peeling) in which the Young's modulus of the photocurable resin layer 25 ′ is lowered, the brittleness is improved and the breakage due to deformation is suppressed and peeled off. Note that a composite method in which the above methods are appropriately combined may be used.

  The concave / convex pattern of the mold 26 is transferred to the photocurable resin layer 25 ′ formed on the front side surface 20 </ b> A of the substrate 20 through the respective steps shown in FIGS. The photocurable resin layer 25 ′ formed on the substrate 20 corresponds to the uneven shape of the mold 26 and the liquid physical properties of the liquid containing the photocurable resin. Since the discharge density of the liquid 25 is optimized, the residue thickness is made uniform, and a preferable concavo-convex pattern without defects is formed.

  Next, a fine pattern is formed on the substrate 20 (or a metal film or the like coated on the substrate 20) using the photocurable resin layer 25 'as a mask.

  When the concavo-convex pattern of the photocurable resin layer 25 ′ on the substrate 20 is transferred, the photocurable resin in the recesses of the photocurable resin layer 25 ′ is removed, and the front side surface 20A or the front side surface 20A of the substrate 20 is removed. The metal layer and the like formed on the substrate are exposed (FIG. 1E: ashing process).

  Further, dry etching is performed using the photocurable resin layer 25 ′ as a mask (FIG. 1 (f): etching step). When the photocurable resin layer 25 ′ is removed, the photocurable resin layer 25 ′ is formed on the photocurable resin layer 25 ′. A fine pattern corresponding to the uneven pattern is formed on the substrate 20.

  In addition, when a metal film or a metal oxide film is formed on the front side surface 20A of the substrate 20, a predetermined pattern is formed on the metal film or the metal oxide film.

  As a specific example of the dry etching, an ion milling method, reactive ion etching (RIE), sputter etching, or the like may be used as long as the photocurable resin layer 25 ′ can be used as a mask. Among these, ion milling and reactive ion etching (RIE) are particularly preferable.

  The ion milling method is also called ion beam etching and introduces an inert gas such as Ar into an ion source to generate ions. This is accelerated through the grid, and collides with the sample substrate for etching.

Examples of the ion source include a Kaufman type, a high frequency type, an electron impact type, a duoplasmatron type, a Freeman type, an ECR (electron cyclotron resonance) type, and the like. Ar gas can be used as a process gas in ion beam etching, and fluorine-based gas or chlorine-based gas can be used as an etchant for RIE.

  As described above, the formation of a fine pattern using the nanoimprint method shown in this example is performed by using the photocurable resin layer 25 ′ to which the concave / convex pattern of the mold 26 is transferred as a mask, and the residual film thickness unevenness and defects due to residual gas. Since the dry etching is performed using the mask without any gap, a fine pattern can be formed on the substrate 20 with high accuracy and high yield.

[Description of nanoimprint system]
Next, a nanoimprint system (nanoimprint apparatus) for realizing the nanoimprint method described above will be described. In the following description, parts that are the same as or similar to those in the previous description are given the same reference numerals, and descriptions thereof are omitted.

(overall structure)
FIG. 2 is a schematic configuration diagram of the nanoimprint system according to the embodiment of the present invention. A nanoimprint system 10 shown in FIG. 1 is disposed on a substrate 20 and a photocurable resin liquid discharge unit 12 that discharges a photocurable resin liquid (resist liquid) onto a substrate 20 having optical transparency such as quartz glass. The pattern transfer unit 14 that transfers a desired pattern to the photocurable resin liquid and the transport unit 22 that transports the substrate 20 are configured.

  The photocurable resin liquid discharge unit 12 includes an inkjet head 24 in which a plurality of nozzles (not shown in FIG. 2, and indicated by reference numeral 23 in FIG. 4) are formed. The photocurable resin liquid 25 is landed on the surface (photocurable resin liquid landing surface) of the substrate 20.

  The pattern transfer unit 14 includes a mold 26 on which a desired concavo-convex pattern to be transferred to the photocurable resin liquid 25 on the substrate 20 is formed, and an ultraviolet irradiation device 28 that irradiates ultraviolet rays, and the photocurable resin liquid. In a state in which the mold 26 is pressed against the surface of the substrate 20 on which 25 has landed, UV irradiation is performed from the back side of the substrate 20 (the surface opposite to the surface where the mold 26 is pressed). By curing the liquid 25, pattern transfer is performed on the photocurable resin liquid 25 (photocurable resin layer 25 ′) on the substrate 20.

  Silicon is applied to the mold 26. Further, since the substrate 20 is made of a light-transmitting material that can transmit ultraviolet rays irradiated from the ultraviolet irradiation device 28, the ultraviolet irradiation device 28 disposed below the substrate 20 (on the side opposite to the mold 26). When the ultraviolet ray irradiation is performed, the photocurable resin liquid 25 on the substrate 20 is irradiated with ultraviolet rays without being blocked by the substrate 20, and the photocurable resin liquid 25 can be cured.

  As the light transmissive material, for example, glass, quartz or the like can be used.

  The mold 26 is configured to be movable in the vertical direction of FIG. 2 (the direction indicated by the double arrow line), and while maintaining the state in which the pattern forming surface of the mold 26 is substantially parallel to the surface of the substrate 20. It moves downward and is pressed against the entire surface of the substrate 20 at substantially the same time, and pattern transfer is performed.

  In addition, although illustration is abbreviate | omitted, the form which comprises the mold 26 with a transparent material and irradiates an ultraviolet-ray from the front side (mold side) of the board | substrate 20 is also possible.

  The transfer unit 22 includes, for example, a transfer unit that fixes and transfers the substrate 20 such as a transfer stage, and holds the substrate 20 on the surface of the transfer unit while holding the substrate 20 on the surface of the photocurable resin liquid discharge unit. The sheet is conveyed in a direction from 12 to the pattern transfer unit 14 (hereinafter, also referred to as “y direction”).

  Specific examples of the conveying means include a combination of a linear motor and an air slider, and a combination of a linear motor and an LM guide. Instead of moving the substrate 20, the photocurable resin liquid discharge unit 12 and the pattern transfer unit 14 may be moved, or both may be moved.

(Description of photocurable resin liquid discharge part)
FIG. 3 is a configuration diagram illustrating a schematic configuration of the photocurable resin liquid discharge unit 12. The photocurable resin liquid discharger 12 shown in the figure includes a serial type ink jet head 24, and the ink jet head 24 is mounted on a carriage 29 that can move along a guide 27 provided along the x direction. ing.

  The photocurable resin liquid discharge unit 12 shown in FIG. 3 discharges the photocurable resin liquid 25 (see FIG. 1) in the x direction while scanning the inkjet head 24 in the x direction, and performs one scan in the x direction. Is completed, the substrate 20 is moved by a predetermined amount in the y direction, the photocurable resin liquid 25 is discharged to the next region, and the photocurable resin liquid 25 is arranged over the entire surface of the substrate 20 while repeating this operation. It is configured.

  4A and 4B are plan views showing an example of nozzle arrangement of the serial type inkjet head 24 shown in FIG. The inkjet head 24 shown in FIG. 4A has a structure in which a plurality of nozzles 23 are arranged along the y direction. Further, as shown in FIG. 4B, it is possible to arrange a plurality of nozzles 23 in a staggered manner to reduce the substantial nozzle pitch in the y direction.

  In this example, the serial type inkjet head 24 is illustrated, but a full-line type inkjet head having a structure in which a plurality of nozzles are arranged over a length corresponding to the entire width of the substrate 20 can also be applied. is there.

  The nozzle arrangement may be a matrix arrangement, a staggered arrangement, or a one-row arrangement.

(Inkjet head structure)
FIG. 5 is a cross-sectional view showing a three-dimensional configuration of a droplet discharge element for one channel of the inkjet head 24. The inkjet head 24 shown in the figure has a structure in which a nozzle plate 23A in which openings of a plurality of nozzles 23 are formed and a flow path plate in which flow paths such as a pressure chamber 32 and a common flow path 35 are formed are laminated and joined. Become.

  The nozzle plate 23 </ b> A constitutes a nozzle surface 23 </ b> B of the inkjet head 24, and a plurality of nozzles 23 communicating with the pressure chambers 32 are formed. In FIG. 5, only one nozzle 23 is shown for the purpose of illustrating one channel.

  The flow path plate forms a side wall portion of the pressure chamber 32 and forms a flow path that forms a supply port 34 as a narrowed portion (most narrowed portion) of an individual supply path that guides ink from the common flow path 35 to the pressure chamber 32. It is a member.

  For convenience of explanation, the flow path plate has a structure in which one or a plurality of substrates are stacked, although it is illustrated schematically in FIG. The nozzle plate 23A and the flow path plate can be processed into a required shape by a semiconductor manufacturing process using silicon as a material.

  The common flow path 35 communicates with an ink tank (not shown) serving as an ink supply source, and ink supplied from the ink tank is supplied to each pressure chamber 32 via the common flow path 35.

  The diaphragm 36 constituting a part of the pressure chamber 32 (the top surface in FIG. 5) is provided with an upper (individual) electrode 37A and a lower (common) electrode 37B, and between the upper electrode 37A and the lower electrode 37B. A piezoelectric element 38 having a structure in which a piezoelectric body 38A is sandwiched between them is joined.

  When the diaphragm 36 is formed of a metal thin film or a metal oxide film, it functions as a common electrode corresponding to the lower electrode 37B of the piezoelectric element 38. In the aspect in which the diaphragm is formed of a non-conductive material such as resin, a lower electrode layer made of a conductive material such as metal is formed on the surface of the diaphragm member.

  By applying a driving voltage to the upper electrode 37A, the piezoelectric element 38 is deformed to change the volume of the pressure chamber 32, and ink is ejected from the nozzles 23 due to the pressure change accompanying this. After the ink is ejected, when the piezoelectric element 38 returns to its original state, new ink is refilled into the pressure chamber 32 from the common flow path 35 through the supply port 34.

(Inkjet head and head cover structure)
In the present embodiment, the temperature of the nozzle plate 23A of the inkjet head 24 (particularly heating) is adjusted for the discharge stability of the photocurable resin liquid and the discharge of fine droplets. The viscosity is lowered. Further, in order to prevent heat generated by adjusting the temperature of the nozzle plate 23A from being transferred to the substrate 20 to which the photocurable resin liquid is applied, a head cover 42 is provided, and the temperature of the head cover 42 is adjusted. Yes.

  6A is a perspective view of the inkjet head 24 and the head cover 42, and FIG. 6B is a cross-sectional view of FIG. 6A.

  As shown in FIG. 6, in this embodiment, a heater 44 and a thermistor 46 are provided on the side surface of the nozzle plate 23A. The temperature of the photocurable resin liquid discharged from the nozzle plate 23A can be warmed by the heater 44, the viscosity of the photocurable resin liquid can be controlled, and the discharge stability and the droplet amount can be controlled. Further, by reducing the droplets, the droplets of the functional material can be densely arranged on the substrate, and the throughput can be improved.

  The temperature of the heater 44 is converted into a temperature by measuring a resistance value with a thermistor 46 provided on the side of the nozzle plate 23A, and the temperature of the heater 44 and the temperature of the photocurable resin liquid are controlled. In the present embodiment, the heater 44 and the thermistor 46 serve as the first temperature control means.

  A head cover 42 is provided around the inkjet head 24 to cover the entire inkjet head 24. The substrate to which the photocurable resin liquid is applied is heated by the heat generated by heating the inkjet head 24, and the apparatus and the substrate are displaced due to the difference in linear expansion, which affects the imprint accuracy. By covering the inkjet head 24 with the head cover 42, it is possible to prevent a temperature difference between the ambient temperature of the inkjet head 24 and the substrate 20, thereby preventing a temperature change of the substrate 20 and imprinting with high accuracy. be able to. In this embodiment, since only the nozzle plate 23A is heated, it is possible to prevent the heat from the first temperature control means from being transmitted to the substrate 20 or another device.

  In FIG. 6, the temperature adjustment using the heater 44 and the thermistor 46 has been described. However, as another mode, the temperature can be controlled by a heater, a thermocouple, and a Peltier element.

  In the head cover 42, in order to prevent the ambient temperature of the inkjet head 24 from being heated by the heat generated in the heater 44 that heats the nozzle plate 23A, a temperature adjusting water flow path 48 is provided to control the temperature of the head cover 42. By (especially cooling), it is possible to prevent the ambient temperature from rising due to the heat of the heater 44.

  As a method of cooling the head cover 42, as shown in FIG. 6, the head cover 42 can be cooled by providing a temperature-regulating water channel 48 and circulating water at a desired temperature through the channel. The temperature adjusting water flow channel 48 is provided with a circulation pump (not shown) and is provided with a radiator to radiate and circulate the heat obtained in the head cover 42 for cooling. Further, the temperature of the water flowing in the temperature adjusting water flow channel 48 is controlled according to the temperature outside the inkjet head 24.

  The head cover 42 can be cooled by air cooling, and can be cooled by directly applying air to the head cover 42. In the present embodiment, the head cover 42 including means for cooling the head cover 42 by water cooling or air cooling serves as the second temperature control means.

  A heat sink can be used as the head cover 42. By using a heat sink, the temperature can be lowered by heat dissipation. As a material of the head cover 42, a metal such as aluminum or copper that easily conducts heat can be used.

  In FIG. 6, the head cover is described so as to cover the surface other than the nozzle plate 23A side of the inkjet head 24. However, if the heat of the heater 44 can be prevented from being transmitted to other devices and substrates, the entire surface is covered. At least one of the surfaces can be controlled in temperature.

  7A and 7B are diagrams of an inkjet head and an inkjet cover according to another embodiment, in which FIG. 7A is a perspective view and FIG. 7B is a cross-sectional view of FIG.

  FIG. 7 is different from the above embodiment in that a heater 50 for heating the inkjet head 24 is provided in addition to the heater 44 for heating the nozzle plate 23A. Since the temperature of the photocurable resin liquid in the pressure chamber 32 can be adjusted by providing the heater 50 that heats the inkjet head 24, the temperature of the photocurable resin liquid discharged more efficiently is controlled. be able to.

  The means heater 50 for adjusting the temperature of the inkjet head 24 and the means for cooling the head cover 42 can have the same configuration as in the above embodiment.

  Next, the configuration of the nozzle cover 52 that prevents the heat of the nozzle surface 23B of the inkjet head 24 from being transferred to the substrate will be described with reference to FIGS.

  FIG. 8 is a cross-sectional view of the inkjet head 24 including a nozzle cover 52 that covers a part of the nozzle surface 23B. As shown in FIG. 8, in order to prevent the heat of the nozzle surface 23B of the inkjet head 24 from being transmitted to the substrate, a nozzle cover 52 that covers a portion other than the nozzle 23 of the nozzle surface 23B can be provided. Covering the nozzle surface 23B can prevent heat generated by heating the nozzle surface 23B from being transmitted to the substrate 20.

  As the nozzle cover 52 that covers the nozzle surface 23B, one that is integral with the head cover 42 can be used as shown in FIG. Further, the nozzle cover 52 can be provided as a separate member from the head cover 42.

  Further, by integrating the nozzle cover 52 and the head cover 42, the temperature of the nozzle cover 52 can be adjusted by the temperature adjusting water flow path 48 provided in the head cover 42. When the nozzle cover 52 and the head cover 42 are separate members, the nozzle cover 52 can be provided with temperature control means. The temperature control means can have the same configuration as the head cover 42.

  As the nozzle cover 52, a heat sink can be used similarly to the head cover 42. By using a heat sink, the temperature can be lowered by heat dissipation. As a material of the nozzle cover 52, a metal such as aluminum or copper that easily conducts heat can be used.

  FIG. 9 is a cross-sectional view showing another embodiment of the nozzle cover 52 covering a part of the nozzle surface 23B. The nozzle cover 52 shown in FIG. 9 is different from the above embodiment in that the nozzle cover 52 is not in contact with the nozzle surface 23B.

  As shown in FIG. 9, since the air insulation layer 53 can be provided between the nozzle surface 23B and the nozzle cover 52 by making the nozzle surface 23B and the nozzle cover 52 non-contact with each other, the heat insulation effect is further improved. It can be demonstrated.

  In the present invention, the nozzle cover 52 may or may not be provided. However, by providing the nozzle cover 52, heat transfer from the nozzle plate 23A to the substrate 20 can be prevented, so that the nozzle cover 52 is provided. Is preferably provided.

  In the embodiment shown in FIGS. 6 to 9, the head cover 42 and the nozzle cover 52 are preferably water-repellent in order to prevent condensation due to a temperature difference. The water repellent treatment can be performed by a method similar to the conventional method.

  Next, a maintenance method for the nozzle surface 23B will be described. As described above, in the present invention, a step is provided between the nozzle plate 23A having the nozzles 23 for discharging the liquid and the nozzle cover 52 that covers the nozzle surface 23B. Then, by setting the liquid discharged by the purge to a predetermined liquid amount, the purged liquid can be absorbed without damaging the nozzle surface 23B.

  10 is a cross-sectional view of the droplet 54 on the nozzle surface 23B discharged by purging, and FIG. 11 is a plan view of the nozzle surface from which the droplet in FIG. 10 was discharged. FIG. 12 is a cross-sectional view of the droplet 54 ′ on the nozzle surface 23 </ b> B according to another embodiment, and FIG. 13 is a plan view of the nozzle surface on which the droplet 54 ′ is purged in FIG. 12.

  As shown in FIGS. 10 and 12, in the present invention, a step is provided between the nozzle plate 23 </ b> A and the nozzle cover 52. By making the height of the purged droplet 54 higher than the step between the nozzle surface 23B and the nozzle cover 52, the droplet purged by the blot member can be absorbed by contacting the blot member.

Also, as shown in FIG. 12, it is preferable that the ink remains on the nozzle plate 23 </ b> A so that the purged droplets of the functional ink do not reach the side surface of the nozzle cover 52. It is not preferable to purge the nozzle cover 52 until the liquid droplets are applied, because the liquid droplets are ejected without staying on the nozzle surface. Specifically, it is preferable to determine the amount of droplets so as to satisfy the following condition.

  When the liquid height is h, the radius is r, the contact angle with the nozzle surface is θ, and the volume of the droplet is V, the following relationship is established.

  As shown in FIGS. 11A and 13A, when the droplets discharged from the nozzles by the purge are independent, assuming that the nozzle interval is d and the width of the nozzle cover is w, 2r <d, 2r < The height of the droplet is adjusted so as to be higher than the level difference between the nozzle surface and the nozzle cover with the amount of droplet satisfying w.

  Further, as shown in FIGS. 11 (b) and 13 (b), when a droplet discharged from a nozzle by purging is connected to a droplet discharged from an adjacent nozzle, the cross-sectional area S is related by the following equation. .

  If the length of the discharged liquid is l, V = S · l. Therefore, the height h of the liquid droplet given by the equation (1) is adjusted so as to be higher than the level difference between the nozzle surface and the nozzle cover with the amount of liquid droplet satisfying 2r <w.

  FIGS. 11A, 11B, 13A, and 13B are plan views of nozzle surfaces having droplets purged from the nozzles. FIGS. 11 (a) and 13 (a) are diagrams showing a state where the purged liquid droplets 54 and 54 ′ are isolated, and FIGS. 11 (b) and 13 (b) are adjacent to each other. FIG. 4 is a diagram in which droplets 54 and 54 ′ purged from a matching nozzle 23 are in contact with each other and formed as a row of droplets. In this embodiment, in any case, the droplet can be absorbed by contacting the blot member. The size of the purged droplet 54 is such that the droplet 54 can be held by the nozzle plate 23A and the height of the droplet 54 can be made higher than the step between the nozzle surface 23B and the nozzle cover 52. good. Specifically, the purge amount of droplets can be determined by the thickness of the nozzle cover 52, the width of the portion of the nozzle plate 23A not covered with the nozzle cover 52, the nozzle pitch, and the contact angle of the nozzle plate 23A.

  Next, a method of absorbing the purged droplet 54 by the blot member 56 will be described with reference to FIGS.

  As shown in FIG. 15, the blot member is formed by providing a cleaning pad 60 on a cylindrical roller 58. As shown in FIG. 14A, when the cleaning pad 60 is brought into contact with the stepped structure of the nozzle plate 23A and the nozzle cover 52, the droplets are absorbed by the cleaning pad 60, and the droplets can be removed. (FIG. 14B).

  The blot member 56 is provided with a cleaning pad 60 on a cylindrical roller 58, and as shown in FIG. 14A, the blot member 56 is brought into contact with the step structure of the nozzle plate 23A and the nozzle cover 52, thereby blotting inside the recess of the step structure. Since the member 56 can be inserted, the purged droplet can be absorbed easily. The blotting member can be absorbed by the cleaning pad 60 by moving the blotting member perpendicularly with respect to the nozzle surface so as to come into contact with the nozzle surface.

  In addition, the cleaning performance can be improved by moving the cleaning pad 60 of the blot member 56 relative to the nozzle surface 23B. As a method of moving the cleaning pad 60, as shown in FIG. 15, the cleaning pad 60 is supplied from a supply roller 62 and taken up by a take-up roller 64 via a roller 58, thereby moving the cleaning pad 60. It is also possible to clean.

  As the cleaning pad 60, Toraysee (Toray Industries, Inc.) or the like can be used.

  14 and 15, the cylindrical roller 58 is used as a member for contacting the cleaning pad 60, but the present invention is not limited to this, and other shapes may be used. As described above, since the purged droplet 54 is formed so as to exit from the recess of the step structure, the droplet 54 can be absorbed even if the blot member 56 does not enter the recess of the step structure. Can do. However, in order to move the cleaning pad that allows the blot member 56 to enter the recess, it is preferable to use a cylindrical roll.

  Also, the blot member 56 heats the nozzle plate 23A when the photocurable resin liquid is discharged, and is transferred to the blot member 56 that wipes off the purged photocurable resin liquid, and the heat is convected to the imprint system. In order to prevent transmission by heat dissipation, it is preferable to adjust the temperature.

  As a method of adjusting the temperature of the blotting member 56, as shown in FIG. 15, the temperature adjustment can be performed by providing a temperature adjusting water flow channel 66 in the roller 58 and flowing a liquid having a predetermined temperature. By adjusting the temperature of the blot member 56, the heat used for heating the nozzle plate can be cooled and can be prevented from being transmitted to other devices. As a method of supplying the temperature adjusting liquid to the blot member 56, a method similar to the method of adjusting the temperature of the head cover 42 can be performed. In the present embodiment, the temperature adjustment water use channel 66 for adjusting the temperature of the blot member 56 is the third temperature control means.

  FIG. 16 is a perspective view of the capping member 68 used when the inkjet head 24 is stored. The inkjet head 24 is provided with a capping member 68 as a means for preventing the nozzle 23 from drying or preventing an increase in ink viscosity near the nozzle.

  The capping member 68 can be moved relative to the inkjet head 24 by a moving mechanism (not shown), and is moved from a predetermined retracted position to a maintenance position below the inkjet head 24 as necessary.

  The capping member 68 is displaced up and down relatively with respect to the inkjet head 24 by an elevator mechanism (not shown). The cap surface is covered with the capping member 68 by raising the cap to a predetermined raised position when the power is turned off or waiting for printing, and bringing the cap into close contact with the inkjet head 24.

  During printing or standby, if the frequency of use of specific nozzles 23 is low and ink is not ejected for a certain period of time, the ink solvent near the nozzles evaporates and the ink viscosity increases. In such a state, ink cannot be ejected from the nozzle 23 even if the piezoelectric element 38 operates.

  Before this state is reached, the piezoelectric element 38 is operated within the range of the viscosity that can be discharged by the operation of the piezoelectric element 38, and is directed toward the capping member 68 to discharge the deteriorated ink near the nozzle whose viscosity has increased. Preliminary discharge is performed. “Preliminary discharge” includes processes called spit, idle discharge, spit discharge, dummy discharge, and the like.

  In addition, when bubbles are mixed in the liquid in the inkjet head 24 or the pressure chamber 32, the ink cannot be ejected from the nozzles 23 even if the piezoelectric element 38 operates. In such a case, the capping member 68 is applied to the inkjet head 24, the ink mixed with the bubbles in the pressure chamber 32 is removed by suction with the suction pump 70, and the suctioned and removed ink is sent to the recovery tank 72. When the suction operation is completed, in order to return the pressure in the capping member 68 to atmospheric pressure, the atmosphere release valve 74 is opened, and the pressure in the capping member 68 is set to atmospheric pressure.

  This suction operation sucks out the deteriorated ink whose viscosity has been increased (solidified) even when the ink-jet head 24 is filled with the initial photo-curable resin liquid or at the start of use after being stopped for a long time. Since the suction operation is performed on the entire photocurable resin liquid in the pressure chamber 32, the consumption amount increases. Therefore, when the increase in the viscosity of the photocurable resin liquid is small, it is preferable to perform preliminary ejection.

  In the present embodiment, as described above, the temperature of the inkjet head 24 or the nozzle plate 23A is adjusted in order to adjust the temperature of the photocurable resin liquid discharged from the inkjet head. Therefore, in order to prevent the heat of the nozzle plate 23A from being transmitted to the capping member 68 and to be transmitted to other devices by convection and heat dissipation, the temperature adjusting water flow path is set so that the temperature of the capping member 68 becomes constant. 76 is provided. The temperature of the capping member 68 can be controlled by flowing a liquid having a predetermined temperature through the temperature adjusting water channel 76. As a method for controlling the temperature of the capping member 68, the same method as that for the head cover 42 and the blot member 56 described above can be used. In the present embodiment, the temperature adjusting water flow path 76 serves as a fourth temperature control means.

  Further, when the nozzle 23 is capped with the capping member 68, it is preferable that the nozzle cover 52 and the capping member 68 are brought into contact with each other for capping. By bringing the capping member 68 into contact with the nozzle cover 52, it is possible to prevent the heat of the nozzle plate 23A from being transmitted to the capping member 68, and to prevent the heat from being transmitted to the substrate and other devices.

[Description of photocurable resin liquid]
Next, as an example of a photocurable resin liquid applied to the nanoimprint system shown in this example, a resist composition (hereinafter, simply referred to as “resist”) will be described in detail.

  The resist composition is a curable composition for imprints containing at least a surfactant containing at least one fluorine, a polymerizable compound, and a photopolymerization initiator I.

  The resist composition aims to develop crosslinkability by having a polyfunctional polymerizable group as a function, or increase the carbon density, increase the total amount of binding energy, or include O, S contained in the cured resin. , N, and the like, may contain a monomer component having one or more functional groups having a polymerizable functional group for the purpose of improving the etching resistance by suppressing the content of a portion having a high electronegativity, and if necessary, A coupling agent with the substrate, a volatile solvent, an antioxidant and the like may be included.

  As the coupling agent with the substrate, the same material as the adhesion treatment agent for the substrate described above can be used. As content, it should just be contained to the extent arrange | positioned in the interface of a board | substrate and a resist layer, it should just be 10 mass% or less, 5 mass% or less is more preferable, 2 mass% or less is still more preferable, Most preferably, it is 0.5 mass% or less.

  The viscosity of the resist composition is determined from the viewpoint of penetration of solids (components excluding volatile solvent components) in the resist composition into the pattern formed in the mold 26 (see FIG. 2) and wetting and spreading to the mold 26. Therefore, the viscosity of the solid content is preferably 1000 mPa · s or less, more preferably 100 mPa · s or less, and even more preferably 20 mPa · s or less. However, when the ink jet method is used, it is preferable that the temperature is controlled at the time of ejection with a room temperature or a head, and it is preferably 20 mPa · s or less, and the surface tension of the resist composition is 20 millinewtons per meter (mN / m ) More than 40 millinewtons per meter, and more preferably from millinewtons per meter to 36 millinewtons per meter, from the viewpoint of securing the ejection stability in the inkjet. For discharging fine droplets, the viscosity is preferably 10 mPa · s or less, and more preferably 6 mPa · s or less.

(Polymerizable compound)
As the polymerizable compound as the main component of the resist composition, the fluorine content in the compound represented by the following [Equation 4] is 5% or less, or a fluoroalkyl group or a fluoroalkyl ether group is substantially included. The polymerizable compound is not included.

  The polymerizable compound is preferably a compound having good quality such as pattern accuracy after curing and etching resistance. The polymerizable compound preferably includes a polyfunctional monomer that is cross-linked by polymerization to become a polymer having a three-dimensional structure, and the polyfunctional monomer includes at least one divalent or trivalent aromatic. It is preferable to have a group.

  In the case of a resist having a three-dimensional structure after curing (polymerization), the shape maintenance property after curing is good, and the stress applied to the resist is concentrated on a specific area of the resist structure due to the adhesive force between the mold and the resist when the mold is peeled off. In addition, the plastic deformation of the pattern is suppressed.

  However, when the ratio of the polyfunctional monomer that becomes a polymer having a three-dimensional structure after polymerization and the density of the site that forms three-dimensional crosslinks after polymerization increase, the Young's modulus after curing increases and the deformability decreases, Moreover, since the brittleness of the film is deteriorated, there is a concern that the film may be easily broken at the time of mold peeling. In particular, in an aspect in which the pattern size is 30 nm width or less and the pattern aspect ratio is 2 or more, and the remaining film thickness is 10 nm or less, when the formation in a wide area such as a hard disk pattern or a semiconductor pattern is attempted, pattern peeling or It is thought that the probability that moge will occur increases.

  Therefore, the polyfunctional monomer is preferably contained in the polymerizable compound in an amount of 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. It has been found that the content is most preferably at least mass%.

Further, it is preferable that the crosslinking density expressed by the following equation [Equation 2] is 0.01 pieces / nm ² or more 10 / nm ² or less, 6 / nm ^{2 hereinafter} 0.1 or / nm ² or more more preferably, it has been found most preferable to be 0.5 or / nm ² to 5.0 pieces / nm ² or less. The cross-linking density of the composition is a value obtained by calculating the cross-linking density of each molecule and further obtaining from the weight average, or measuring the density after curing of the composition, and averaging the respective values for Mw and (Nf-1). And the following equation [Equation 5].

  However, Da is the crosslinking density of one molecule, Dc is the density after curing, Nf is the number of acrylate functional groups contained in one monomer molecule, Na is the Avogadro constant, and Mw is the molecular weight.

  The polymerizable functional group of the polymerizable compound is not particularly limited, but a methacrylate group and an acrylate group are preferable, and an acrylate group is more preferable because of good reactivity and stability.

  The dry etching resistance can be evaluated by the Onishi parameter and the ring parameter of the resist composition. The smaller the Onishi parameter and the larger the ring parameter, the better the dry etching resistance. In the present invention, the resist composition has an Onishi parameter of 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less, and a ring parameter of 0.1 or more, preferably 0.8. Those that are 2 or more, more preferably 0.3 or more are suitable.

  The above parameters are the material parameter values calculated by using the calculation formula described later based on the structural formula for the constituent materials other than the volatile solvent component constituting the resist composition, and the entire composition based on the composition weight ratio. Calculated as an averaged value. Accordingly, the polymerizable compound that is the main component of the resist composition is also preferably selected in consideration of the other components in the resist composition and the above parameters.

Onishi parameter = (total number of atoms in compound) / {(number of carbon atoms in compound) − (number of oxygen atoms in compound)}
Ring parameter = (mass of carbon forming the ring structure) / (total mass of compound)
Examples of the polymerizable compound include the polymerizable monomers shown below and oligomers obtained by polymerizing several units of such polymerizable monomers. From the viewpoint of pattern formability and etching resistance, at least one of the polymerizable monomer (Ax) and the compounds described in paragraphs [0032] to [0053] of JP-A-2009-218550 is used. It is preferable to include.

(Polymerizable monomer (Ax))
The polymerizable monomer (Ax) is represented by the general formula (I) shown in the following [Chemical Formula 1].

In the general formula (I) shown in the above [Chemical Formula 1], Ar represents a divalent or trivalent aromatic group which may have a substituent, X represents a single bond or an organic linking group, R ¹ represents a hydrogen atom or an alkyl group which may have a substituent, and n represents 2 or 3.

  In the above general formula (I), Ar represents a divalent aromatic group (that is, an arylene group) when n = 2, and represents a trivalent aromatic group when n = 3. Examples of the arylene group include hydrocarbon-based arylene groups such as a phenylene group and a naphthylene group; heteroarylene groups in which indole, carbazole and the like are linked groups, preferably a hydrocarbon-based arylene group, and more preferably a viscosity, From the viewpoint of etching resistance, it is a phenylene group. The arylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, a cyano group, an alkoxycarbonyl group, an amide group, and a sulfonamide group.

  Examples of the organic linking group for X include an alkylene group, an arylene group, and an aralkylene group, which may contain a hetero atom in the chain. Among these, an alkylene group and an oxyalkylene group are preferable, and an alkylene group is more preferable. X is particularly preferably a single bond or an alkylene group.

R ¹ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. When R ¹ has a substituent, preferred substituents are not particularly limited, and examples thereof include a hydroxyl group, a halogen atom (excluding fluorine), an alkoxy group, and an acyloxy group. n is 2 or 3, preferably 2.

  The polymerizable monomer (Ax) is a polymerizable monomer represented by the following general formula (Ia) or (Ib) represented by the following [Chemical Formula 2]: This is preferable from the viewpoint of reducing the viscosity.

In the above general formulas (Ia) and (Ib), X ¹ and X ² are each independently an alkylene group which may have a single bond or a substituent having 1 to 3 carbon atoms. R ¹ represents a hydrogen atom or an alkyl group which may have a substituent.

In the general formula (Ia), X ¹ is preferably a single bond or a methylene group, and more preferably a methylene group from the viewpoint of viscosity reduction. The preferable range of X ^{2 is the same as} the preferable range of X ¹ .

R ¹ has the same meaning as R ¹ as in the above formula (I), and preferred ranges are also the same. When the polymerizable monomer (Ax) is liquid at 25 ° C., it is preferable that generation of foreign matters can be suppressed even when the addition amount is increased. The polymerizable monomer (Ax) preferably has a viscosity at 25 ° C. of less than 70 mPa · s from the viewpoint of pattern formation, more preferably 50 mPa · s or less, and particularly preferably 30 mPa · s or less. preferable.

Specific examples of preferred polymerizable monomers (Ax) are shown in the following [Chemical Formula 3]. R ¹ has the same meaning as R ¹ in the general formula (I). R ¹ is preferably a hydrogen atom from the viewpoint of curability.

  Among these, the compound shown in the following [Chemical Formula 4] is particularly preferable because it is liquid at 25 ° C., has a low viscosity, and exhibits better curability.

  In the resist composition, from the viewpoint of improving the composition viscosity, dry etching resistance, imprint suitability, curability and the like, a polymerizable monomer (Ax) and a polymerizable monomer described below as necessary It is preferable to use in combination with another polymerizable monomer different from (Ax).

(Other polymerizable monomers)
Examples of other polymerizable monomers include polymerizable unsaturated monomers having 1 to 6 ethylenically unsaturated bond-containing groups; compounds having an oxirane ring (epoxy compounds); vinyl ether compounds; styrene derivatives; A compound having an atom; propenyl ether, butenyl ether and the like can be mentioned, and a polymerizable unsaturated monomer having 1 to 6 ethylenically unsaturated bond-containing groups is preferable from the viewpoint of curability.

  Among these other polymerizable monomers, from the viewpoints of imprint suitability, dry etching resistance, curability, viscosity, and the like, described in paragraphs [0032] to [0053] of JP-A-2009-218550 A compound can be included more preferably. Furthermore, the polymerizable unsaturated monomer (1-6 functional polymerizable unsaturated monomer) which has 1-6 the said ethylenically unsaturated bond containing group which can be contained is demonstrated.

  First, specific examples of the polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer) include 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2 -Hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) Acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxy Butyl (medium ) Acrylate, acrylic acid dimer, benzyl (meth) acrylate, 1- or 2-naphthyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate , Ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate , Isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclohentanyl (meth) acrylate, dicyclopentanyloxye (Meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol ( (Meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) ) Acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxyethyl (meth) ) Acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) Acrylate, stearyl (meth) acrylate, EO modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, p -Isopropenylphenol, styrene, α-methylstyrene, acrylonitrile are exemplified.

  Among these, a monofunctional (meth) acrylate having an aromatic structure and / or an alicyclic hydrocarbon structure is particularly preferable from the viewpoint of improving dry etching resistance. Specific examples benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl (meth) acrylate are preferred, and benzyl (meth) acrylate is particularly preferred preferable.

  It is also preferable to use a polyfunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups as the other polymerizable monomer. Examples of the bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups that can be preferably used include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, Di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO modified 1,6-hexanediol di (meth) acrylate, ECH modified 1 , 6-hexanediol di (meth) acrylate, allyloxy polyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, modified Bisfeneau A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, ECH-modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO-modified neo Pentyl glycol diacrylate, propylene oxide (hereinafter referred to as “PO”) modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (meta) ) Acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) (Meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH-modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol di (meth) ) Acrylate, tetraethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylol propane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified tripropylene glycol Di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinylethylene urea, Divinyl propylene urea is exemplified.

  Among these, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like are preferably used in the present invention.

  Examples of the polyfunctional polymerizable unsaturated monomer having 3 or more ethylenically unsaturated bond-containing groups include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meta) ) Acrylate, pentaerythritol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylol Propane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) Acrylate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) Examples include acrylate, pentaerythritol ethoxytetra (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

  Among these, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are preferably used in the present invention.

  Examples of the compound having an oxirane ring (epoxy compound) include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycol, and polyglycidyl ethers of aromatic polyols. And hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.

  Specific examples of the compound having an oxirane ring (epoxy compound) include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, bromine Bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether , Glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene group Polydiglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin; Diglycidyl esters of basic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; glycidyl esters of higher fatty acids, etc. Is mentioned.

  Among these, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are preferred.

  Commercially available products that can be suitably used as the glycidyl group-containing compound include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200, (manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Denka Kogyo ( Product)). These can be used individually by 1 type or in combination of 2 or more types.

  The production method of these compounds having an oxirane ring is not limited. For example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The chemistry ofheterocyclic compounds-Small RingHeterocycles part3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesive, Vol. 30, No. 5, 42, 1986, Yoshimura, Adhesive No. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-100308, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.

  As other polymerizable monomer used in the present invention, a vinyl ether compound may be used in combination. As the vinyl ether compound, known compounds can be appropriately selected. For example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylol Propane trivinyl ether, trimethylol ethane trivinyl ether, hexanediol divinyl ether, tetra Tylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether , Trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, 1,1,1-to Scan [4- (2-vinyloxy ethoxy) phenyl] ethane, bisphenol A divinyloxyethyl carboxyethyl ether.

  These vinyl ether compounds can be obtained, for example, by the method described in Stephen C. Lapin, Polymer Paint Color Journal. 179 (4237), 321 (1988), that is, the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or various methods. They can be synthesized by a reaction of a monohydric alcohol or a polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used alone or in combination of two or more.

  Further, as other polymerizable monomer, a styrene derivative can also be employed. Examples of styrene derivatives include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, p-hydroxy. Examples include styrene.

  In addition, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl ( Use compounds containing fluorine atoms such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, etc. Can do.

  As other polymerizable monomer, propenyl ether and butenyl ether can also be used. Examples of the propenyl ether or butenyl ether include 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-norbornene, 1-4-di (1-butenoxy) butane, 1,10-di (1-butenoxy) decane, 1,4-di (1-butenoxymethyl) cyclohexane, diethylene glycol di (1-butenyl) ether, 1,2,3-tri (1-butenoxy) propane, propenyl ether propylene Carbonate or the like can be suitably applied.

(Fluorine-containing surfactant)
In the imprint system shown in this example, since the fluorine-containing surfactant is a part of the resist pattern, the fluorine-containing surfactant has a good pattern forming property, a mold release property after curing, and a resist property with a good etching resistance. Preferably there is.

  In the resist composition, the content of the fluorine-containing surfactant is, for example, 0.001% by mass to 5% by mass, preferably 0.002% by mass to 4% by mass, and more preferably 0%. 0.005 mass% or more and 3 mass% or less. When using 2 or more types of surfactant, the total amount becomes the said range. When the surfactant is in the range of 0.001% by mass to 5% by mass in the composition, the effect of coating uniformity is good, and deterioration of mold transfer characteristics due to excessive surfactant or after imprinting It is difficult to cause deterioration of etching suitability in the etching process.

(Polymerization initiator I)
The polymerization initiator I is not particularly limited as long as it generates an active species that is activated by the light L1 used when the resist composition is cured to start polymerization of a polymerizable compound contained in the resist composition. As the polymerization initiator I, a radical polymerization initiator is preferable. Moreover, in this invention, the polymerization initiator I may use multiple types together.

  As the polymerization initiator I, acylphosphine oxide compounds and oxime ester compounds are preferable from the viewpoint of curing sensitivity and absorption characteristics, and for example, those described in paragraph [0091] of JP-A No. 2008-105414 are preferable. Can be adopted.

  The content of the polymerization initiator I in the entire composition excluding the solvent is, for example, 0.01% by mass or more and 15% by mass or less, preferably 0.1% by mass or more and 12% by mass or less, more preferably It is 0.2 mass% or more and 7 mass% or less. When using 2 or more types of photoinitiators, the total amount becomes the said range.

  When the content of the photopolymerization initiator is 0.01% by mass or more, the sensitivity (fast curability), resolution, line edge roughness, and coating strength tend to be improved, which is preferable. On the other hand, when the content of the photopolymerization initiator is 15% by mass or less, light transmittance, colorability, handleability and the like tend to be improved, which is preferable.

  Up to now, various addition amounts of preferred photopolymerization initiators have been studied for ink-jet compositions and dye- and / or pigment-containing compositions for liquid crystal display color filters, but for photo-imprints such as imprints. There is no report about the preferable addition amount of the photopolymerization initiator for the curable composition. That is, in a system containing a dye and / or pigment, the initiator may act as a radical trapping agent, which affects the photopolymerization and sensitivity. In consideration of this point, the amount of the photopolymerization initiator added is optimized in these applications. On the other hand, in the resist composition, dyes and / or pigments are not essential components, and the optimal range of the photopolymerization initiator may be different from those in the fields of inkjet compositions, liquid crystal display color filter compositions, and the like. .

  As the radical photopolymerization initiator contained in the resist applied to the imprint system shown in this example, acylphosphine compounds and oxime ester compounds are preferable from the viewpoints of curing sensitivity and absorption characteristics. As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. As these examples, for example, those described in paragraph [0091] of JP-A No. 2008-105414 can be preferably used.

  Note that the light L1 includes radiation in addition to light of wavelengths in the ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, and other electromagnetic fields, and electromagnetic waves. Examples of the radiation include microwaves, electron beams, EUV, and X-rays. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light with a plurality of different wavelengths (composite light). The exposure can be multiple exposure, and the entire surface can be exposed after forming a pattern for the purpose of increasing the film strength and etching resistance.

  The photopolymerization initiator I must be selected in a timely manner with respect to the wavelength of the light source to be used, but is preferably one that does not generate gas during mold pressurization and exposure. When the gas is generated, the mold is contaminated, so that the mold must be frequently cleaned, and the resist composition is deformed in the mold and the transfer pattern accuracy is deteriorated.

  In the resist composition, the polymerizable monomer contained is preferably a radical polymerizable monomer, and the photopolymerization initiator I is preferably a radical polymerization initiator that generates radicals upon light irradiation.

(Other ingredients)
As already described, the resist composition applied to the imprint system shown in this example is based on various purposes in addition to the above-described polymerizable compound, fluorine-containing surfactant, and photopolymerization initiator I. Other components such as a surfactant, an antioxidant, a solvent, and a polymer component may be included as long as the effects of the present invention are not impaired. The outline of other components will be described below.

(Antioxidant)
The resist composition can contain a known antioxidant. Content of antioxidant is 0.01 mass% or more and 10 mass% or less with respect to a polymerizable monomer, for example, Preferably it is 0.2 mass% or more and 5 mass% or less. When using 2 or more types of antioxidant, the total amount becomes the said range.

The antioxidant suppresses fading caused by heat or light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). In particular, in the present invention, by adding an antioxidant, there is an advantage that coloring of a cured film can be prevented and a reduction in film thickness due to decomposition can be reduced. Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, hindered phenol antioxidants and thioether antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness.

  Commercially available products of the antioxidant include trade names Irganox 1010, 1035, 1076, 1222 (above, manufactured by Ciba Geigy Co., Ltd.), trade names Antigene P, 3C, FR, Sumilyzer S, Sumilyzer GA80 (Sumitomo Chemical Co., Ltd.) Product name) ADK STAB AO70, AO80, AO503 (manufactured by ADEKA Corporation) and the like. These may be used alone or in combination.

(Polymerization inhibitor)
The resist composition preferably contains a small amount of a polymerization inhibitor. The content of the polymerization inhibitor is 0.001% by mass or more and 1% by mass or less, more preferably 0.005% by mass or more and 0.5% by mass or less, and still more preferably with respect to the total polymerizable monomer. By blending an appropriate amount of a polymerization inhibitor that is 0.008% by mass or more and 0.05% by mass or less, a change in viscosity over time can be suppressed while maintaining high curing sensitivity.

(solvent)
The resist composition can contain various solvents as required. A preferable solvent is a solvent having a boiling point of 80 to 280 ° C. at normal pressure. Any solvent can be used as long as it can dissolve the composition, but a solvent having any one or more of an ester structure, a ketone structure, a hydroxyl group, and an ether structure is preferable. Specifically, preferred solvents are propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, gamma butyrolactone, propylene glycol monomethyl ether, ethyl lactate alone or a mixed solvent, and a solvent containing propylene glycol monomethyl ether acetate. Most preferable from the viewpoint of coating uniformity.

  The content of the solvent in the resist composition is optimally adjusted depending on the viscosity of the components excluding the solvent, coating properties, and the desired film thickness. From the viewpoint of improving coating properties, 0 to 99% by mass in the total composition. Is preferable, and 0 to 97 mass% is more preferable. In particular, when a pattern with a film thickness of 500 nm or less is formed, it is preferably 20% by mass or more and 99% by mass or less, more preferably 40% by mass or more and 9% by mass or less, and particularly preferably 70% by mass or more and 98% by mass or less.

(Polymer component)
In the resist composition, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer having a molecular weight higher than that of the other polyfunctional polymerizable monomer may be blended within a range that achieves the object of the present invention. Examples of the polyfunctional oligomer having photoradical polymerizability include various acrylate oligomers such as polyester acrylate, urethane acrylate, polyether acrylate, and epoxy acrylate. The addition amount of the oligomer component is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, and most preferably 0 to 5% by mass with respect to the component excluding the solvent of the composition. %.

  The resist composition may contain a polymer component from the viewpoint of improving dry etching resistance, imprint suitability, curability and the like. Such a polymer component is preferably a polymer having a polymerizable functional group in the side chain. The weight average molecular weight of the polymer component is preferably from 2,000 to 100,000, more preferably from 5,000 to 50,000, from the viewpoint of compatibility with the polymerizable monomer.

  The addition amount of the polymer component is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 10% by mass, and most preferably 2% by mass or less, relative to the component excluding the solvent of the composition. It is. From the viewpoint of pattern formability, the content of the polymer component having a molecular weight of 2000 or more is preferably 30% by mass or less in the resist composition except for the solvent. The resin component is preferably as few as possible, and it is preferable that the resin component is not included except for a surfactant and a trace amount of additives.

  In addition to the above-described components, the resist composition may include a release agent, a silane coupling agent, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, an adhesion promoter, a thermal polymerization initiator, and a coloring agent. Agents, elastomer particles, photoacid growth agents, photobase generators, basic compounds, flow regulators, antifoaming agents, dispersants, and the like may be added.

  The resist composition can be prepared by mixing the above-described components. Moreover, after mixing each component, it can also prepare as a solution by filtering with a filter with the hole diameter of 0.003 micrometer-5.0 micrometers, for example. Mixing and dissolution of the curable composition for photoimprint is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can be refiltered. The material of the filter used for filtration may be polyethylene resin, polypropylene resin, fluorine resin, nylon resin or the like, but is not particularly limited.

  Such a resist composition is adjusted to have a viscosity within a range in which micro droplets can be formed by an ink jet method. The range of the viscosity that can be ejected by the ink jet method is 4 to 20 millipascal second, and preferably 8 to 15 millipascal second. The amount of solvent at this time is 10 weight percent or less. The increase in viscosity when the solvent volatilizes over time is set to 10 millipascal seconds or less.

  The surface tension of the resist composition adjusted to a viscosity suitable for the ink jet system as described above is 20 millinewtons per meter to 40 millinewtons per meter, preferably 25 millinewtons per meter to 35 millinewtons per meter. It is as follows.

  In the said embodiment, although the nanoimprint system 10 provided with the photocurable resin liquid discharge part 12 and the pattern transfer part 14 was illustrated, the photocurable resin liquid discharge part 12 and the pattern transfer part 14 are comprised as a separate apparatus. Embodiments are possible.

  That is, as the nanoimprint system (apparatus) 10 according to the present invention, a configuration including a photocurable resin liquid discharge device and a pattern transfer device is also possible.

  The functional liquid ejecting apparatus, the imprint system, and the functional liquid ejecting method according to the present invention can be suitably used in the following manufacturing.

  The first technique is a case where a molded shape (pattern) itself has a function and can be applied as various nanotechnology element parts or structural members. Examples include various micro / nano optical elements, high-density recording media, optical films, and structural members in flat panel displays.

  The second technology is to build a multilayer structure by simultaneous integral molding of microstructure and nanostructure and simple interlayer alignment, and apply this to the production of μ-TAS (Micro-Total Analysis System) and biochips. It is what.

  The third technique is used for processing a substrate by a method such as etching using the formed pattern as a mask. In this technology, high-precision alignment and high integration enable high-density semiconductor integrated circuit fabrication, liquid crystal display transistor fabrication, and magnetic media for next-generation hard disks called patterned media instead of conventional lithography technology. It can be applied to processing.

  Furthermore, microelectromechanical systems (MEMS), sensor elements, optical components such as diffraction gratings and relief holograms, nanodevices, optical devices, optical films and polarizing elements for the production of flat panel displays, thin film transistors for liquid crystal displays, organic transistors , Color filter, overcoat layer, pillar material, rib material for liquid crystal alignment, microlens array, immunoassay chip, DNA separation chip, microreactor, nanobiodevice, optical waveguide, optical filter, photonic liquid crystal, antireflection structure It is also useful in permanent film formation applications such as (moth eye).

  As described above, the nanoimprint system (apparatus) has been described in detail as a specific example of the liquid ejection apparatus, the liquid ejection method, and the nanoimprint system according to the present invention. However, the present invention is not limited to the above examples, and the gist of the present invention. Various improvements and modifications may be made without departing from the scope.

  DESCRIPTION OF SYMBOLS 10 ... Nanoimprint system (apparatus), 12 ... Photocurable resin liquid discharge part, 14 ... Pattern transfer part, 20 ... Board | substrate, 22 ... Conveyance part, 23 ... Nozzle, 23A ... Nozzle plate, 23B ... Nozzle surface, 24 ... Inkjet Head, 25 ... Photo-curable resin liquid, 26 ... Mold, 28 ... Ultraviolet irradiation device, 32 ... Pressure chamber, 38 ... Piezoelectric element, 42 ... Head cover, 44, 50 ... Heater, 46 ... Thermistor, 48, 66, 76 ... Temperature control water channel, 52 ... Nozzle cover, 53 ... Thermal insulation layer, 54 ... Droplet, 56 ... Blot member, 58 ... Roller, 60 ... Cleaning pad, 62 ... Supply roller, 64 ... Winding roller, 68 ... Capping 70, suction pump, 72 ... collection tank, 74 ... air release valve

Claims (12)

A liquid ejection head comprising a nozzle plate on which nozzles for ejecting functional liquid onto a substrate are formed, and provided with a piezoelectric element for pressurizing the functional liquid in a pressure chamber communicated with the nozzle;
Relative movement means for relatively moving the substrate and the liquid ejection head;
A transfer means for transferring the concavo-convex pattern of the mold having a predetermined concavo-convex pattern formed on the surface of the substrate on which the functional liquid has landed;
Curing means for curing the functional liquid in a state where the entire surface of the mold on which the uneven pattern is formed is in contact with the functional liquid;
First temperature control means for controlling the temperature of the nozzle plate;
An imprint system comprising: a cover that covers at least one surface other than the nozzle plate of the liquid discharge head, and second temperature control means for controlling the temperature of the cover.   The said 1st temperature control means is provided with a means to control the temperature of the side surface of the said liquid discharge head, and controls the temperature of the said functional liquid in the said liquid discharge head. Imprint system.   The second temperature control means is a liquid discharge head cover including a surface of the liquid discharge head other than the nozzle plate and a flow path that covers the first temperature control means and distributes the temperature control liquid. The imprint system according to claim 1 or 2.   The imprint system according to any one of claims 1 to 3, wherein the nozzle is made of silicon.   The imprint system according to claim 1, further comprising a nozzle cover that covers a portion of the nozzle plate where the nozzle is not formed.   The imprint system according to claim 5, wherein the nozzle cover is formed at a position closer to the substrate than the nozzle plate.   The imprint system according to claim 1, wherein a vacuum is formed between the nozzle plate and the substrate. A maintenance method for an imprint system according to claim 6 or 7,
A functional liquid discharging step of purging the functional liquid;
An absorption step of absorbing the functional liquid by bringing a blotting member into contact with the functional liquid attached to the nozzle plate by the functional liquid discharging step;
The imprint system maintenance method according to claim 1, wherein the droplets attached to the nozzle plate have a height higher than a thickness of the nozzle cover and are not in contact with the nozzle cover.   The imprint system maintenance method according to claim 8, wherein the blot member and the liquid ejection head are relatively moved after the blot member is brought into contact with the functional liquid.   The imprint system according to claim 8 or 9, further comprising third temperature control means for controlling a temperature of the blot member, wherein the temperature of the blot member is controlled to substantially the same temperature as the substrate. Maintenance method.   The capping member that covers the nozzle during standby of the liquid discharge head is provided, and the capping member is brought into contact with the nozzle cover to perform capping of the nozzle. The maintenance method for the imprint system according to item 1.   The said capping member is provided with the 4th temperature control means which controls the temperature of the said capping member, The temperature of the said capping member is controlled to substantially the same temperature as the said board | substrate, The Claim 8 to 11 characterized by the above-mentioned. The imprint system maintenance method according to any one of the preceding claims.

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